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Results for “surface reconstruction kinetics”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Verification and validation of linear gyrokinetic and kinetic-MHD simulations for internal kink instability in DIII-D tokamak

Here, verification and linear validation of the internal kink instability in tokamak have been performed for both gyrokinetic (GTC) and kinetic-MHD codes (GAM-solver, M3D-C1-K, NOVA, XTOR-K). Using realistic magnetic geometry and plasma profiles from the same equilibrium reconstruction of the DIII-D shot #141216, these codes exhibit excellent agreement for the growth rate and mode structure of the internal kink mode when all kinetic effects are suppressed. The simulated radial mode structures, obtained from linear simulations, are in reasonable agreement with the normalised electron cyclotron emission measurement after adjusting, within the experimental uncertainty, the safety factor q = 1 flux-surface location in the equilibrium reconstruction. Compressible magnetic perturbations strongly destabilize the kink, while poloidal variations of the equilibrium current density reduce the growth rate of the kink. Furthermore, kinetic effects of thermal ions are found to decrease the kink growth rate in kinetic-MHD simulations, but increase the kink growth rate in gyrokinetic simulations, due to the additional drive of the ion temperature gradient and parallel electric field. Kinetic thermal electrons are found to have negligible effects on the internal kink instability.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Mechanistic and Kinetic Analysis of Complete Methane Oxidation on a Practical PtPd/Al 2 O 3 Catalyst

A PtPd/Al 2 O 3 catalyst developed for the complete oxidation of methane from the ventilation air of underground coal mines is compared against a model PdO/Al 2 O 3 catalyst. Although the PtPd/Al 2 O 3 catalyst is substantially more active and stable than the model catalyst, the nature of active sites between the two catalysts is deemed to be fundamentally the same based on their response to different feed gas compositions and the evolution of surface CO adsorption complexes during time-resolved CO adsorption DRIFTS experiment. For both catalysts, coordinatively unsaturated Pd sites are considered the active centers for methane activation and the subsequent oxidation reaction. H 2 O competes with CH 4 for the same active sites, resulting in severe inhibition. Additionally, the CH 4 oxidation reaction also causes self-inhibition. Taking both inhibition effects into consideration, a relatively simple kinetic model is developed. The model provides a good fit of the 72 sets of kinetic data collected on the PtPd/Al 2 O 3 catalyst under practically relevant reaction conditions with CH 4 concentration in the range of 0.05–0.4%, H 2 O concentration of 1.0–5.0%, and reaction temperatures of 450–700 °C. Kinetic parameters based on the model suggest that the CH 4 activation energy on the PtPd/Al 2 O 3 catalyst is 96.7 kJ/mol, and the H 2 O adsorption energy is –31.0 kJ/mol. Both values are consistent with the parameters reported in the literature. The model can be used to develop catalyst sizing guidelines and be incorporated into the control algorithm of the catalytic system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Kinetically Dormant Ni‐Rich Layered Cathode During High‐Voltage Operation

Abstract The degradation of Ni‐rich cathodes during long‐term operation at high voltage has garnered significant attention from both academia and industry. Despite many post‐mortem qualitative structural analyses, precise quantification of their individual and coupling contributions to the overall capacity degradation remains challenging. Here, by leveraging multiscale synchrotron X‐ray probes, electron microscopy, and post‐galvanostatic intermittent titration technique, the thermodynamically irreversible and kinetically reversible capacity loss is successfully deconvoluted in a polycrystalline LiNi 0.83 Mn 0.1 Co 0.07 O 2 cathode during long‐term charge/discharge cycling in full cell configuration. Contradicting the dramatic capacity loss, the layered structure remains highly alive even after 1000 cycles at 4.6 V while undergoing a three‐order of magnitude reduction in the mass transfer kinetics, leading to almost fully recoverable capacity under kinetic‐free conditions. Such kinetic dormant behavior after cycling is not simply ascribed to poor chemical diffusion by reconstructed cathode surface but highly synchronizes with the lattice strain evolution stemming from the structural heterogeneity between deeply delithiated layered and degraded rock‐salt phases at high voltage. These findings deepen the degradation mechanism of high‐voltage cathodes to achieve long‐cycling and fast‐charging performance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Crystallization Mechanisms of Poly(vinylidene Fluoride- co -chlorotrifluoroethylene): Nucleation Transitions, Growth Kinetics, and Microstructure Evolution

The crystallization kinetics of FK-800, a commercial semicrystalline copolymer of chlorotrifluoroethylene and vinylidene fluoride (poly(CTFE-co-VDF)), dictate its microstructure and functional performance. Crystallization occurs between the glass transition (T g ≈ 31 °C) and melting point (T m ≈ 110 °C), with grain boundaries playing a key role in applications such as memristors, where they regulate filament growth. This study integrates in situ atomic force microscopy (AFM), grazing-incidence wide-angle X-ray scattering (GIWAXS), and differential scanning calorimetry (DSC) to characterize nucleation, growth, and morphology across the full crystallization window. Hot-stage AFM reveals a transition from homogeneous to heterogeneous nucleation near 45 °C and a shift from reaction-limited to diffusion-limited growth above 60 °C. Kinetics are analyzed using Lauritzen–Hoffman, Turnbull–Fisher, and Avrami models to extract surface free energies and activation barriers. A multiscale modeling framework is developed in which nucleation densities and growth rates measured by AFM are used to reconstruct Avrami kinetics, which are then validated against coverage data, and extrapolated to predict bulk crystallization behavior observed by DSC. GIWAXS confirms a primarily flat-on chain orientation at all temperatures, linking orientation to domain morphology. This integrative approach quantitatively connects nanoscale crystallization dynamics with macroscopic phase evolution, establishing a quantitative framework for modeling crystallization across time, temperature, and length scales.

Crystallization↗
DOE OSTI2025

Lewis Acid Site Engineering in Chromite Spinels Orchestrated Surface Reconstruction and Surpasses RuO 2 in Oxygen Evolution

Atomic-scale engineering of chromite spinels featuring redox-active tetrahedral A-sites and strong Cr–O covalency offers a promising route to superior platinum-group-metal-free oxygen evolution reaction (OER) catalysts. However, comprehensive studies addressing how cation substitution influences surface chemistry and governs OER activity and durability in chromite spinels remain limited. Here, in this work, a systematic investigation of the multicationic chromite series Ni x Fe y Cr 3−x−y O 4 is presented, identifying composition-dependent Lewis acidity as a descriptor of superior OER performance. It is further demonstrated that tuning surface acidity directly controls dynamic reconstruction processes and lattice-oxygen participation during spinel-based electrocatalysis. Following activation, the optimized Ni 0.8 Fe 0.3 Cr 1.9 O 4 catalyst delivers a current density of 10 mA cm −2 at an overpotential of 235 mV, surpassing RuO 2 , with excellent long-term stability. Integrating microscopic and spectroscopic analysis with operando impedance spectroscopy, it shows that activation generates an oxyhydroxide overlayer and reveals a previously unrecognized link between surface Lewis acidity and the growth kinetics and activity of these shells. Density functional theory calculations indicate that Fe incorporation at octahedral sites raises the O 2p-band center and lowers oxygen-vacancy formation energy, promoting lattice-oxygen activation and triggering reconstruction, yielding enhanced OER. This work integrates cation-driven surface-acidity modulation, acidity-governed reconstruction, and OER activity enhancement into a unified predictive framework for designing earth-abundant spinel-based catalysts.

operando impedance spectroscopy↗
DOE OSTI2025

How transparent is graphene? A surface science perspective on remote epitaxy

Remote epitaxy is the synthesis of a single crystalline film on a graphene-covered substrate, where the film adopts epitaxial registry to the substrate as if the graphene is transparent. Despite many exciting applications for flexible electronics, strain engineering, and heterogeneous integration, an understanding of the fundamental synthesis mechanisms remains elusive. Here we offer a perspective on the synthesis mechanisms, focusing on the foundational assumption of graphene transparency. We identify challenges for quantifying the strength of the remote substrate potential that permeates through graphene, and propose Fourier and beating analysis as a bias-free method for decomposing the lattice potential contributions from the substrate, from graphene, and from surface reconstructions, each at different frequencies. We highlight the importance of graphene-induced reconstructions on epitaxial templating, drawing comparison to moiré epitaxy. We highlight the role of the remote potential in tuning surface diffusion and adatom kinetics on graphene, which are crucial for navigating the competition between remote epitaxy and defect-seeded mechanisms like pinhole epitaxy. In light of this weak remote potential, we re-evaluate the current state-of-the-art experimental evidence, highlighting why it remains challenging to experimentally validate a ‘remote’ epitaxy mechanism that cannot be explained by alternatives, such as pinhole-seeded epitaxy or serial van der Waals epitaxy. We end with one experimental example that, to out knowledge, cannot be explained by competing mechanisms: a different long-range epitaxial relationship for GdPtSb films grown on graphene/sapphire, compared to direct epitaxy on sapphire. We suggest for future experiments that directly measure the remote potential and impact of tuneable growth kinetics.

epitaxy↗
DOE OSTI2022

Reaction processes at step edges on S-decorated Cu(111) and Ag(111) surfaces: MD analysis utilizing machine learning derived potentials

We report a variety of complexation, reconstruction, and sulfide formation processes can occur at step edges on the {111} surfaces of coinage metals (M) in the presence of adsorbed S under ultra-high vacuum conditions. Given the cooperative many-atom nature of these reaction processes, Molecular Dynamics (MD) simulation of the associated dynamics is instructive. However, only quite restricted Density Functional Theory (DFT)-level ab initio MD is viable. Thus, for M = Ag and Cu, we instead utilize the DeePMD framework to develop machine-learning derived potentials, retaining near-DFT accuracy for the M–S systems, which should have broad applicability. These potentials are validated by comparison with DFT predictions for various key quantities related to the energetics of S on M(111) surfaces. The potentials are then utilized to perform extensive MD simulations elucidating the above diverse restructuring and reaction processes at step edges. Key observations from MD simulations include the formation of small metal–sulfur complexes, especially MS 2 ; development of a local reconstruction at A-steps featuring an S-decorated {100} motif; and 3D sulfide formation. Additional analysis yields further information on the kinetics for metal–sulfur complex formation, where these complexes can strongly enhance surface mass transport, and on the propensity for sulfide formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Irreversible Catalyst Deactivation Mechanisms of PdO/γ-Al 2 O 3 Catalysts for Lean Methane Oxidation

PdO/γ-Al 2 O 3 catalysts suffer from gradual and irreversible catalyst deactivation under lean CH 4 oxidation conditions, especially in a wet feed. Here, time-resolved CO chemisorption DRIFTS measurements are conducted systematically on a series of PdO/γ-Al 2 O 3 catalysts to probe the surface reactivity of PdO nanoparticles after various in situ pretreatments. At 80 °C, CO barely adsorbs on fully oxidized PdO surfaces but interacts with coordinatively unsaturated Pd sites, causing gradual reduction of the PdO surfaces. This results in the formation of characteristic IR bands on various metallic Pd 0 sites. By monitoring and comparing the formation kinetics of these IR bands on samples before and after CH 4 oxidation, we theorize that the irreversible catalyst deactivation during CH 4 oxidation is caused by PdO surface reconstruction, in which coordinatively unsaturated Pd sites gradually become fully coordinated by oxygen. Effectively, the surface reconstruction leads to the formation of a passivation layer on the PdO nanoparticles, which hinders their ability in activating CH 4 , and hence the subsequent oxidation reaction. Temperature-programmed reduction with CO as the reductant (CO-TPR) reveals that the passivation layer formed during CH 4 oxidation is significant enough to increase the reduction temperature of PdO nanoparticles of the 3.0% PdO/γ-Al 2 O 3 samples, although such an effect is less obvious for the 0.4% PdO/γ-Al 2 O 3 samples. On the other hand, it is also discovered that the passivation layer is not completely inert. Under certain reaction conditions, with some being relatively mild, such as low-temperature CO oxidation in a net lean atmosphere and in the presence of H 2 O, the passivation layer can undergo structure change which results in regeneration or even activation of CH 4 oxidation activity of an already deactivated catalyst. Additionally, it is discovered that the fully coordinated Pd–O surface is a metastable phase under CH 4 oxidation conditions. In the presence of H 2 O and at ambient temperatures, surfaces with coordinatively unsaturated Pd sites are thermodynamically more favorable.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Bayesian Learning of Adatom Interactions from Atomically Resolved Imaging Data

Atomic structures and adatom geometries of surfaces encode information about the thermodynamics and kinetics of the processes that lead to their formation, and which can be captured by a generative physical model. In this work, we develop a workflow based on a machine-learning-based analysis of scanning tunneling microscopy images to reconstruct the atomic and adatom positions, and a Bayesian optimization procedure to minimize statistical distance between the chosen physical models and experimental observations. We optimize the parameters of a 2- and 3-parameter Ising model describing surface ordering and use the derived generative model to make predictions across the parameter space. For concentration dependence, we compare the predicted morphologies at different adatom concentrations with the dissimilar regions on the sample surfaces that serendipitously had different adatom concentrations. The proposed workflow can be used to reconstruct the thermodynamic models and associated uncertainties from the experimental observations of materials microstructures. The code used in the manuscript is available at https://github.com/saimani5/Adatom_interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Bulk Stoichiometry-Controlled Surface Reconstruction of Nanosized Ni−In Intermetallic Catalysts Steers Methanol Selectivity in CO2 Hydrogenation

Intermetallic compounds (IMCs) are attractive platforms for elucidating structure−catalysis relationships due to their ordered atomic structure and well-defined bulk composition. Yet, how their surfaces reconstruct under reaction conditions and how such reconstruction is governed by bulk stoichiometry remain poorly understood. Here, we show that SiO2-supported Ni−In IMCs undergo reaction-driven surface reconstruction during CO2 hydrogenation and that bulk stoichiometry can be used to steer this evolution toward methanol formation. Among the compositions examined (Ni2In1, Ni1In1, Ni2In3, and Ni1In2), Ni2In3/SiO2 exhibits the highest methanol selectivity (∼70%) and a methanol space-time yield of 652 mg·gmetal−1·h−1 at 250 °C and 30 bar. Combined structural, surface characterization, and kinetic analyses suggest that the intermetallic bulk remains largely preserved, whereas the surface departs from the stoichiometric bulk and evolves toward InOx-enriched surface domains coupled to an electron-rich Ni−In intermetallic phase. The extent of this evolution depends strongly on the bulk Ni:In stoichiometry and is most pronounced for Ni2In3/SiO2. These findings identify bulk stoichiometry as a handle for tuning the working-state surface of intermetallic catalysts and provide a basis for designing methanol synthesis catalysts through controlled surface reconstruction.

Wang, Caiqi [ORNL] (ORCID:0000000198849990)↗
NASA NTRS2013

Powered Flight Design and Reconstructed Performance Summary for the Mars Science Laboratory Mission

The Powered Flight segment of Mars Science Laboratory's (MSL) Entry, Descent, and Landing (EDL) system extends from backshell separation through landing. This segment is responsible for removing the final 0.1% of the kinetic energy dissipated during EDL and culminating with the successful touchdown of the rover on the surface of Mars. Many challenges exist in the Powered Flight segment: extraction of Powered Descent Vehicle from the backshell, performing a 300m divert maneuver to avoid the backshell and parachute, slowing the descent from 85 m/s to 0.75 m/s and successfully lowering the rover on a 7.5m bridle beneath the rocket-powered Descent Stage and gently placing it on the surface using the Sky Crane Maneuver. Finally, the nearly-spent Descent Stage must execute a Flyaway maneuver to ensure surface impact a safe distance from the Rover. This paper provides an overview of the powered flight design, key features, and event timeline. It also summarizes Curiosity's as flown performance on the night of August 5th as reconstructed by the flight team.

Mars Science Laboratory (MSL)↗
DOE OSTI2021

Spin pinning effect to reconstructed oxyhydroxide layer on ferromagnetic oxides for enhanced water oxidation

Producing hydrogen by water electrolysis suffers from the kinetic barriers in the oxygen evolution reaction (OER) that limits the overall efficiency. With spin-dependent kinetics in OER, to manipulate the spin ordering of ferromagnetic OER catalysts (e.g., by magnetization) can reduce the kinetic barrier. However, most active OER catalysts are not ferromagnetic, which makes the spin manipulation challenging. In this work, we report a strategy with spin pinning effect to make the spins in paramagnetic oxyhydroxides more aligned for higher intrinsic OER activity. The spin pinning effect is established in oxideFM/oxyhydroxide interface which is realized by a controlled surface reconstruction of ferromagnetic oxides. Under spin pinning, simple magnetization further increases the spin alignment and thus the OER activity, which validates the spin effect in rate-limiting OER step. The spin polarization in OER highly relies on oxyl radicals (O∙) created by 1 st dehydrogenation to reduce the barrier for subsequent O-O coupling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Improving LiNiO 2 cathode performance through particle design and optimization

We report to enable further development of Ni-rich LiNi x Mn y Co 1-x-y O 2 (NMC, x ≥ 0.9) cathodes for commercial applications, fundamental understanding of the synthesis–property–performance relationships in the LiNiO 2 (LNO) parent phase is essential. In the present study, we report synthesis approaches to produce well-formed, similar-sized single-crystal LiNiO 2 (SC-LNO) with different shapes and dominating surface facets, and reveal the dependence of cathode rate performance and cycling stability on particle morphology and surface. While octahedron-shaped SC-LNO with the (012) surface shows better rate capability and improved ability in utilizing the kinetically slow anodic process in the 3.5 V region, cubic-shaped SC-LNO with the (104) surface delivers superior cycling stability, especially upon cycling at a high upper cutoff voltage of 4.6 V. Improvement in cycling stability is correlated with reduced surface reconstruction and preferential LiF formation through the interaction with the electrolyte on the (104) surface. Our study not only demonstrates the importance of particle morphology and surface design, it also provides key insights into desirable material properties for developing future LNO-based cathode materials with better performance.

25 ENERGY STORAGE↗
DOE OSTI2024

Measurement of 3 Λ H production in Pb–Pb collisions at √ s NN = 5.02 TeV

The first measurement of 3 Λ H and $^{3}_{\overline{Λ}}$$\overline{H}$ differential production with respect to transverse momentum and centrality in Pb–Pb collisions at √ s NN = 5.02 TeV is presented. The 3 Λ H has been reconstructed via its two-charged-body decay channel, i.e., 3 Λ H → 3 He → π - . A Blast-Wave model fit of the p T -differential spectra of all nuclear species measured by the ALICE collaboration suggests that the kinetic freeze-out surface is consistent with that of other nuclei. The ratio between the integrated yields of 3 Λ H and 3 He is compared to predictions from the statistical hadronisation model and the coalescence model, with the latter being favoured by the presented measurements.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Modification of the magneto-hydrodynamic equilibrium by the lower-hybrid wave driven fast electrons on the TST-2 spherical tokamak

Presence of a large population of fast particles may qualitatively modify the tokamak equilibrium from the one that can be described by standard magneto-hydrodynamics (MHD). The kinetic modification of the MHD equilibrium was studied for a lower-hybrid (LH) wave driven plasma on the TST-2 spherical tokamak. The analysis was performed using an equilibrium reconstruction method based on an extended MHD model that considers a two-component plasma of bulk MHD fluid and kinetic fast electrons. Scrape-off-layer current appeared naturally in the extended MHD analysis because of the finite electron orbit excursion from the flux surfaces. This reduced the bulk pressure contribution to the toroidal current substantially. Furthermore, the resulting poloidal flux profile was more consistent with that inferred from the Thomson scattering measurement.

extended magneto-hydrodynamics↗
DOE OSTI2024

Intermittent oxidation kinetics and metal/oxide interfacial undulation

The phenomenon of oxygen-adsorption-induced surface restructuring is widespread across various metal-oxygen systems, yet its impact on initiating bulk oxide formation remains largely unexplored. In this study, through in-situ atomic-resolution electron microscopy observations of surface oxidation of Cu(110) and Cu 85 Au 15 (110), we unveil intermittent oxide-film growth modulated by oxygen-induced surface restructuring. This modulation is evidenced by repeated pinning of Cu 2 O growth front at isolated Cu columns of the c(6×2)-O reconstruction, owing to required long-range diffusion of Cu and O atoms to the Cu 2 O growth front. We reveal that Cu vacancies, generated at the Cu 2 O growth front, are injected into the Cu 2 O/Cu interface, inducing hill-and-valley undulation of the Cu 2 O film. In contrast, atomic vacancies produced during the Cu 85 Au 15 (110) oxidation preferentially migrate into interfaces between Au-rich and Au-poor regions in the bulk, resulting in a flat and adherent Cu 2 O film. These findings demonstrate the critical role of oxygen-induced surface restructuring in modulating oxide-film-growth kinetics and manipulability of the fate of injected vacancies by alloying, thereby offering insights applicable to a broader range of metal-oxygen systems for fine-tuning oxidation kinetics and enhancing oxide/metal interfacial adhesion.

25 ENERGY STORAGE↗
NASA NTRS2017

Decoupled Method for Reconstruction of Surface Conditions From Internal Temperatures On Ablative Materials With Uncertain Recession Model

Obtaining measurements of flight environments on ablative heat shields is both critical for spacecraft development and extremely challenging due to the harsh heating environment and surface recession. Thermocouples installed several millimeters below the surface are commonly used to measure the heat shield temperature response, but an ill-posed inverse heat conduction problem must be solved to reconstruct the surface heating environment from these measurements. Ablation can contribute substantially to the measurement response making solutions to the inverse problem strongly dependent on the recession model, which is often poorly characterized. To enable efficient surface reconstruction for recession model sensitivity analysis, a method for decoupling the surface recession evaluation from the inverse heat conduction problem is presented. The decoupled method is shown to provide reconstructions of equivalent accuracy to the traditional coupled method but with substantially reduced computational effort. These methods are applied to reconstruct the environments on the Mars Science Laboratory heat shield using diffusion limit and kinetically limited recession models.

Oliver, A. Brandon↗
DOE OSTI2026

CO (2) Electroreduction on Borated Copper Surfaces: Boron Active Sites, Not Copper

Boron-doped copper has recently emerged as an active and stable catalyst for the electrochemical reduction of CO 2 to value-added C 2 products. Here, in this work, we develop a realistic model of CO electroreduction on surface borides of copper under operational conditions, taking into account the effects of electrode potential, electrolyte environment, and pH. We study the possible reconstruction of the electrocatalyst surface using grand canonical DFT and global optimization to obtain a potential-dependent grand canonical ensemble description of metastable, hydrogen-covered catalyst surfaces. Two key surface configurations, low H coverage (LC, −0.6 V SHE ) and high H coverage (HC, −0.8 V SHE ), dominate this ensemble, with the former being kinetically persistent and C 2 selective under strongly reducing conditions. Nonmetallic boron sites on the surface copper boride are found to bind CO more strongly than copper sites, and mechanistic investigation of CO electroreduction pathways presents a surprisingly unconventional case of boron-centered reactivity in contrast to typical copper-centered reactivity. Neighboring boron sites present along boron chains on the surface copper boride are found to facilitate C−C coupling, thereby driving the high C 2 selectivity of this electrocatalyst.

boron-doped copper↗